DE69909272T2 - SULFUR-CONTAINING ADDITIONAL COMPOUNDS OF POLYTHIOLES AND NORBORN DERIVATIVES, METHOD FOR THE PRODUCTION THEREOF AND THEIR APPLICATION FOR THE PRODUCTION OF RADICALLY NETWORKED PRODUCTS - Google Patents

Abstract

Sulphur product, (P), process for making (P), films, molded articles made therefrom, wherein (P) is obtained by the addition reaction of at least one polythiol (I) with at least one compound of formula (II):in which R1 represents a linear or branched aliphatic residue comprising an ethylenic unsaturation double bond, it being optional for the latter to be that by which R1 is connected to the norbornene ring, it also being optional for the said ring to comprise other substituents chosen from C1-C3 alkyl groups, in proportions corresponding or substantially corresponding to one thiol group of the polythiol or polythiols (I) per mole of the compound or compounds (II), the thiol groups of the compound or compounds (I) adding predominantly to the cyclic double bond of the compound or compounds (II) and, on average, one ethylenic unsaturation of a compound (II) of the two which it carries remaining free; or sulphur product, (P'), obtained by the addition reaction of at least one polythiol (I) with at least one sulphur product (P), the double bonds of the said sulphur product (P) having been completely or substantially completely consumed, the sulphur product (P') obtained being a crosslinked product.

Description

The present invention relates to new sulfur-containing products by adding at least one polythiol at least one norbornene derivative with an exocyclic ethylenic unsaturation are available; a process for producing these sulfur-containing products; a radically cross-linkable composition that such sulfur-containing product in the crosslinkable state and the resulting networked products and their manufacture.

The present invention aims expanding the range of these sulfur-containing products in different areas, namely optical materials, coatings and adhesives, are of interest, and where the mechanical properties dependent on can vary from polythiol.

For optical applications are particularly desirable products that are radically, in particular photochemically, crosslinkable and so cross-linked materials with high refractive index result, whereby one specifically aimed at products with the highest possible sulfur content, to further improve the refractive index of these materials.

Products of the reaction of polythiols with unsaturated alicyclic compounds with at least two unsaturations per molecule, at least one of which is a cyclic unsaturation are already have been generally described.

• – die direkte Vernetzung einer Mischung aus Polythiol und Vinylnorbornen nicht immer möglich ist: die Mischung aus den getesteten Tri- oder Tetrathiolen und Vinylnorbornen war zweiphasig; die getesteten Dithiole ergaben mit Vinylnorbornen eine homogene Mischung, konnten aber bei Zugabe eines Photoinitiators nicht unter UV vernetzt werden;
• – die thermische Umsetzung eines Polythiols mit Dicyclopentadien mit einer Thiolgruppe pro Mol Dicyclopentadien führt zu einem Produkt, das unter UV mit einem Polythiol als Vernetzer nicht vernetzt.

However, our own research showed that:

• - The direct crosslinking of a mixture of polythiol and vinyl norbornene is not always possible: the mixture of the tri- or tetrathiols and vinyl norbornene tested was two-phase; the dithiols tested gave a homogeneous mixture with vinyl norbornene, but could not be crosslinked under UV when a photoinitiator was added;
• - The thermal reaction of a polythiol with dicyclopentadiene with one thiol group per mole of dicyclopentadiene leads to a product that does not crosslink under UV with a polythiol as a crosslinking agent.

In view of this situation now surprisingly discovered that one special family of compounds, namely substituted norbornenes with an exocyclic unsaturation, with polythiols under stoichiometric Conditions of one or about a thiol group per mole of the norbornene addition products in question result, which subsequently in the presence of at least one polythiol UV and generally can be radically networked.

One can thus substances with high Produce sulfur content that meets the desired goals by one first a cross-linkable, liquid sulfur-containing product (P) that produces the starting material for the Formulation of a product (P ') or one in the desired one Shape, namely as a film or molded part, forms a crosslinkable composition. The sulfur-containing product (P) is not with the disadvantages of Polythiols and norbornene derivatives used in its manufacture afflicted, which are volatile, toxic products with unpleasant smell. When formulating the product (P ') or the crosslinkable Composition must therefore only non-toxic products with a slight odor be handled.

From DATABASE CHEMABS CHEMICAL ABSTRACTS SERVICE, COLUMBUS, OHIO, US, STN, accession number 114: 248656, XP002090932, is the use of addition products of ethylidene-5-norbornen-2 and tetrakis (mercaptoacetate-3) pentaerythritol with a molar ratio of 0.5 / 1 (i.e. 4 SH functions per double bond) as multifunctional Crosslinker (polythiol) known.

Products are from US-A-3 734 986 (Dithiols) known from the reaction of vinylcyclohexene with a dithiol.

The production of stable addition products polythiols with dienes of the norbornene type with terminal double bonds, either by further addition of polythiol or by radical Polymerization are crosslinkable, is thus known in these two Publications not described.

• (A) mit mindestens einer Verbindung der Formel (II):
  
  worin R¹ für einen linearen oder verzweigten aliphatischen Rest mit einer ethylenisch ungesättigten Doppelbindung steht, wobei R¹ über letztere an den Norbornenring gebunden sein kann und der Ring auch andere, unter C₁-C₃-Alkyl ausgewählte Substituenten enthalten kann, in Anteilen, die zumindest im wesentlichen einer Thiolgruppe des bzw. der Polythiole (I) pro Mol der Verbindung bzw. Verbindungen (II) entsprechen, wobei die Thiolgruppen der Verbindung bzw. Verbindungen (I) sich hauptsächlich an die cyclische Doppelbindung der Verbindung bzw. Verbindungen (II) addieren und durchschnittlich eine der beiden ethylenischen Ungesättigtheiten einer Verbindung (II) frei bleibt; oder
• (B) mit mindestens einem gemäß obigem Punkt (A) erhaltenen vernetzbaren Produkt (P), wobei die Doppelbindungen des Produkts (P) vollständig oder im wesentlichen vollständig verbraucht worden sind und es sich bei dem Produkt (P') um ein vernetztes Produkt handelt.

The present invention therefore relates to a sulfur-containing product obtainable by addition reaction of at least one polythiol (I)

• (A) with at least one compound of the formula (II):
  
  in which R ^{1 represents} a linear or branched aliphatic radical with an ethylenically unsaturated double bond, where R ¹ can be bonded to the norbornene ring via the latter and the ring can also contain other substituents selected from C ₁ -C ₃ alkyl, in proportions, which correspond at least essentially to one thiol group of the polythiol (s) (I) per mole of the compound or compounds (II), the thiol groups of the compound or compounds (I) mainly being cyclic Add the double bond of the compound or compounds (II) and on average one of the two ethylenic unsaturations of a compound (II) remains free; or
• (B) with at least one crosslinkable product (P) obtained according to item (A) above, the double bonds of the product (P) having been completely or substantially completely used up and the product (P ') being a crosslinked product ,

With the one or more to manufacture the networked product (P ') The polythiols (I) used do not necessarily have to be the act the same polythiols that are used to produce the crosslinkable Product (P) have been used.

The networked product (P ') is used in the case that this crosslinkable product (P) a functionality of ethylenic unsaturation of at least 3, with a polythiol (I) with an SH functionality of at least 2 and in the event that crosslinkable product (P) a functionality of ethylenic unsaturation of at least 2, with a polythiol (I) with an SH functionality of at least 3 receive. When using polythiol mixtures for crosslinking amounts their average SH functionality is at least 2.

When compound of formula (II) it is especially 5-vinyl-2-norbornene (5-vinylbicyclo [2.2.1] hept-2-ene) or 5-ethylidene-2-norbornene (5-ethylidene bicyclo [2.2.1] hept-2-ene).

• – R² für einen aliphatischen, aromatischen oder heterocyclischen oder eine Kombination daraus enthaltenden n-wertigen Rest steht, der Substituenten enthalten kann, wobei das Gerüst oder die Substituenten durch mindestens ein, unter -O- oder -S- ausgewähltes Heteroatom und/oder eine unter
  
  ausgewählte Gruppe unterbrochen sein können, und
• – n für eine ganze Zahl von 2 bis 6 steht.

The polythiols (I) are selected in particular from the compounds of the formula R ² - [--SH] _n , where:

• - R ^{2 stands} for an aliphatic, aromatic or heterocyclic or a combination thereof containing n-valent radical, which may contain substituents, the framework or the substituents being substituted by at least one heteroatom selected from -O- or -S- and / or one under
  
  selected group can be interrupted, and
• - n represents an integer from 2 to 6.

The polythiols (I) can be polythiols which are obtained by adding a polythiol of the formula R ² - [--SH] _n , in which R ² and n have the meaning given above, to a compound of the formula (II) The above definition with an excess of thiol and under addition conditions in which no crosslinking occurs on the basis of the Makosco-Miller relationship (Macromolecules, 1976, Volume 9, pages 199-211) can be obtained.

• (1) aliphatische Polythiole, wie Methandithiol, 1,2-Ethandithiol, 1,1-Propandithiol, 1,3-Propandithiol, 2,2-Propandithiol, 1,6-Hexandithiol, 1,2,3-Propantrithiol, 1,1-Cyclohexandithiol, 1,2-Cyclohexandithiol, 2,2-Dimethylpropan-l,3-dithiol, 3,4-Dimethoxybuten-1,2-dithiol, Bicyclo[2.2.1]heptan-exo-cis-2,3-dithiol, 1,1-Bis(mercaptomethyl)cyclohexan, Thioäpfelsäurebis(2-mercaptoethylester), 2,3-Dimercaptobernsteinsäure-2-mercaptoethylester, 2,3-Dimercapto-1-propanol-2-mercaptoacetat, 2,3-Dimercapto-1-propanol-3-mercaptopropionat, Diethylenglykolbis(2-mercaptoacetat), Diethylenglykolbis(3-mercaptopropionat), 1,2-Dimercaptopropylmethylether, 2,3-Dimercaptopropylmethylether, 2,2-Bis(mercaptomethyl)-1,3- propandithiol, Bis(2-mercaptoethyl)ether, Ethylenglykolbis(2-mercaptoacetat), Ethylenglykolbis(3-mercaptopropionat), Trimethylolpropantris(3-mercaptopropionat), Trimethylolpropantris(2-mercaptoacetat), Pentaerythrittetrakis(3-mercaptopropionat), Pentaerythrittetrakis(2-mercaptoacetat), Polyethylenglykoldimercaptoacetate und Polyethylenglykoldi(mercaptopropionate) sowie durch Halogen, wie Chlor und Brom, substituierte Derivate dieser Verbindungen;
• (2) aromatische Polythiole, wie 1,2-Dimercaptobenzol, 4-t-Butyl-1,2-benzoldithiol, 1,3-Dimercaptobenzol, 1,4-Dimercaptobenzol, 1,2-Bis(mercaptomethyl)benzol, 1,3-Bis(mercaptomethyl)benzol, 1,4-Bis(mercaptomethyl)benzol, 1,2-Bis(mercaptoethyl)benzol, 1,3-Bis(mercaptoethyl)benzol, 1,4-Bis(mercaptoethyl)benzol, 1,2-Bis(mercaptomethylenoxy)benzol, 1,3-Bis(mercaptomethylenoxy)benzol, 1,4-Bis(mercaptomethylenoxy)benzol, 1,2-Bis(mercaptoethylenoxy)benzol, 1,3-Bis(mercaptoethylenoxy)benzol, 1,4-Bis(mercaptoethylenoxy)benzol, 1,2,3-Trimercaptobenzol, 1,2,4-Trimercaptobenzol, 1,3,5-Trimercaptobenzol, 1,2,3-Tris(mercaptomethyl)benzol, 1,2,4-Tris(mercaptomethyl)benzol, 1,3,5-Tris(mercaptomethyl)benzol, 1,2,3-Tris(mercaptoethyl)benzol, 1,2,4-Tris(mercaptoethyl)benzol, 1,3,5-Tris(mercaptoethyl)benzol, 1,2,3-Tris(mercaptomethylenoxy)benzol, 1,2,4-Tris(mercaptomethylenoxy)benzol, 1,3,5-Tris(mercaptomethylenoxy)benzol, 1,2,3-Tris(mercaptoethylenoxy)benzol, 1,2,4-Tris(mercaptoethylenoxy)benzol, 1,3,5-Tris(mercaptoethylenoxy)benzol, 1,2,3,4-Tetramercaptobenzol, 1,2,3,5-Tetramercaptobenzol, 1,2,4,5-Tetramercaptobenzol, 1,2,3,4-Tetrakis(mercaptomethyl)benzol, 1,2,3,5-Tetrakis(mercaptomethylbenzol), 1,2,4,5-Tetrakis(mercaptomethyl)benzol, 1,2,3,4-Tetrakis(mercaptoethyl)benzol, 1,2,3,5-Tetrakis(mercaptoethyl)benzol, 1,2,4,5-Tetrakis(mercaptoethyl)benzol, 1,2,3,4-Tetrakis(mercaptomethylenoxy)benzol, 1,2,3,5-Tetrakis(mercaptomethylenoxy)benzol, 1,2,4,5-Tetrakis(mercaptomethylenoxy)benzol, 1,2,3,4-Tetrakis(mercaptoethylenoxy)benzol, 1,2,3,5-Tetrakis(mercaptoethylenoxy)benzol, 1,2,4,5-Tetrakis(mercaptoethylenoxy)benzol, 2,2'-Dimercaptobiphenyl, 4,4'-Dimercaptobiphenyl, 4,4'-Dimercaptodibenzyl, 2,5-Toluoldithiol, 3,4-Toluoldithiol, 1,4-Naphthalindithiol, 1,5-Naphthalindithiol, 2,6-Naphthalindithiol, 2,7-Naphthalindithiol, 2,4-Dimethylbenzol-l,3-dithiol, 4,5-Dimethylbenzol-1,3-dithiol, 9,10-Anthracendimethanthiol, 1,3-Di(pmethoxyphenyl)propan-2,2-dithiol, 1,3-Diphenylpropan-2,2-dithiol, Phenylmethan-1,1-dithiol und 2,4-Di(p-mercaptophenyl)pentan;
• (3) halognierte aromatische Polythiole, u. a. chlorierte und bromierte aromatische Polyole, wie 2,5-Dichlorbenzol-1,3-dithiol, 1,3-Di(p-chlorphenyl)propan-2,2-dithiol, 3,4,5-Tribrom-1,2-dimercaptobenzol und 2,3,4,6-Tetrachlor-1,5-bis(mercaptomethyl)benzol;
• (4) heterocyclische Polythiole, wie 2-Methylamino-4,6-dithiol-sym-triazin, 2-Ethylamino-4,6-dithiol-symtriazin, 2-Amino-4,6-dithiol-sym-triazin, 2-Morpholino-4,6-dithiol-sym-triazin, 2-Cyclohexylamino-4,6-dithiol-sym-triazin, 2-Methoxy-4,6-dithiol-sym-triazin, 2-Phenoxy-4,6-dithiol-symtriazin, 2-Thiobenzoloxy-4,6-dithiol-sym-triazin, 2-Thiobutyloxy-4,6-dithiol-sym-triazin und 2-Thiobutyloxy-4,6-dithiol-sym-triazin sowie durch Halogen, wie Chlor und Brom, substituierte Derivate dieser Verbindungen;
• (5) Polythiole, die zusätzlich zu den Mercaptogruppen noch mindestens ein Schwefelatom enthalten, u. a.:
• (5a) aromatische Polythiole, wie 1,2-Bis(mercaptomethylthio)benzol, 1,3-Bis(mercaptomethylthio)benzol, 1,4-Bis(mercaptomethylthio)benzol, 1,2-Bis(mercaptoethylthio)benzol, 1,3-Bis(mercaptoethylthio)benzol, 1,4-Bis(mercaptoethylthio)benzol, 1,2,3-Tris(mercaptomethylthio)benzol, 1,2,4-Tris(mercaptomethylthio)benzol, 1,3,5-Tris(mercaptomethylthio)benzol, 1,2,3-Tris(mercaptoethylthio)benzol, 1,2,4-Tris(mercaptoethylthio)benzol, 1,3,5-Tris(mercaptoethylthio)benzol, 1,2,3,4-Tetrakis(mercaptomethylthio)benzol, 1,2,3,5-Tetrakis(mercaptomethylthio)benzol, 1,2,4,5-Tetrakis(mercaptomethylthio)benzol, 1,2,3,4-Tetrakis(mercaptoethylthio)benzol, 1,2,3,5-Tetrakis(mercaptoethylthio)benzol, 1,2,4,5-Tetrakis(mercaptoethylthio)benzol und am aromatischen Ring dieser Polythiole alkylierte Derivate sowie 4,4'-Thiodibenzolthiol;
• (5b) aliphatische Polythiole, wie Bis(mercaptomethyl)sulfid, Bis(2-mercaptoethyl)sulfid, Bis (2-mercaptopropyl)sulfid, Bis(mercaptomethylthio)methan, Bis(2-mercaptoethylthio)methan, Bis(3-mercaptopropylthio)methan, Tetrakis(7-mercapto-2,5-dithiaheptyl)methan, 1,2-Bis(mercaptomethylthio)ethan, 1,2-Bis(2-mercaptoethylthio)ethan, 1,2-Bis(3-mercaptopropylthio)ethan, 1,3-Bis(mercaptomethylthio)propan, 1,2-Bis (2-mercaptoethylthio)propan, 1,2-Bis(3-mercaptopropylthio)propan, 1,2,3-Tris(mercaptomethylthio)propan, 1,2,3-Tris(2-mercaptoethylthio)propan, 1,2,3-Tris(3-mercaptopropylthio)propan, Tetrakis(mercaptomethylthiomethyl)methan, Tetrakis(2-mercaptoethylthiomethyl)methan, Tetrakis(3-mercaptopropylthiomethyl)methan, Bis(2,3-dimercaptopropyl)sulfid, 2,5-Dimercapto-1,4-dithian, Bis(mercaptomethyl)disulfid, Bis(mercaptoethyl)disulfid und Bis(mercaptopropyl)disulfid, Ester der Thioglykolsäure und Mercaptopropionsäure mit diesen Verbindungen, Hydroxymethylsulfidbis(2- mercaptoacetat), Hydroxymethylsulfidbis(3-mercaptopropionat), Hydroxyethylsulfidbis(2-mercaptoacetat), Hydroxyethylsulfidbis(3-mercaptopropionat), Hydroxypropylsulfidbis(2-mercaptoacetat), Hydroxypropylsulfidbis(3-mercaptopropionat), Hydroxymethyldisulfidbis(2-mercaptoacetat), Hydroxymethyldisulfidbis(3-mercaptopropionat), Hydroxyethyldisulfidbis(2-mercaptoacetat), Hydroxyethyldisulfidbis(3-mercaptopropionat), Hydroxypropyldisulfidbis(2-mercaptoacetat), Hydroxypropyldisulfidbis(3-mercaptopropionat), 2-Mercaptoethyletherbis(2-mercaptoacetat), 2-Mercaptoethyletherbis(3-mercaptopropionat), 1,4-Dithian-2,5-diolbis(3-mercaptopropionat), Thioglykolsäurebis(2-mercaptoethylester), Thiodipropionsäurebis(2-mercaptoethylester), 4,4'-Thiodibuttersäurebis(2-mercaptoethylester), Dithiodiglykolsäurebis(2-mercaptoethylester), Dithiodipropionsäurebis(2-mercaptoethylester), 4,4'-Dithiodibuttersäurebis(2-mercaptoethylester), Thiodiglykolsäurebis(2,3-dimercaptopropylester), Thiodipropionsäurebis(2,3-dimercaptopropylester), Dithiodiglykolsäurebis(2,3-dimercaptopropylester) und Dithiodipropionsäurebis(2,3-dimercaptopropylester) sowie durch Halogen, wie Chlor und Brom, substituierte Derivate dieser Verbindungen; 4-Mercaptomethyl-3,6-dithia-1,8-octandithiol; und
• (5c) heterocyclische Verbindungen, wie 3,4-Thiophendithiol, 2,5-Bis(mercaptomethyl)tetrahydrothiophen, Bis(mercaptomethyl)-1,3-dithiolan, 2,5-Dimercapto-1,3,4-diazol, 2,5-Dimercapto-1,4-dithian und 2,5-Dimercaptomethyl-1,4-dithian sowie durch Halogen, wie Chlor und Brom, substituierte Derivate dieser Verbindungen; und Tris(3-mercaptopropyl)isocyanurat; und
• (6) Produkte der Reaktion von Polythiolen mit mehrfach ungesättigten Verbindungen (SH-Überschuß/Ungesättigtheiten), wie die Additionsprodukte von 5-Ethyliden-2-norbornen oder Diclyclopentadien und Pentaerythrittetrakis(mercaptoacetat).

Examples of polythiols are:

• (1) aliphatic polythiols such as methanedithiol, 1,2-ethanedithiol, 1,1-propanedithiol, 1,3-propanedithiol, 2,2-propanedithiol, 1,6-hexanedithiol, 1,2,3-propanetrithiol, 1,1 -Cyclohexanedithiol, 1,2-cyclohexanedithiol, 2,2-dimethylpropane-l, 3-dithiol, 3,4-dimethoxybutene-1,2-dithiol, bicyclo [2.2.1] heptane-exo-cis-2,3-dithiol , 1,1-bis (mercaptomethyl) cyclohexane, thio-malic acid bis (2-mercaptoethyl ester), 2,3-dimercapto-succinic acid-2-mercaptoethyl ester, 2,3-dimercapto-1-propanol-2-mercaptoacetate, 2,3-dimercapto-1- propanol-3-mercaptopropionate, diethylene glycol bis (2-mercaptoacetate), diethylene glycol bis (3-mercapto propionate), 1,2-dimercaptopropyl methyl ether, 2,3-dimercaptopropyl methyl ether, 2,2-bis (mercaptomethyl) -1,3-propanedithiol, bis (2nd -mercaptoethyl) ether, ethylene glycol bis (2-mercaptoacetate), ethylene glycol bis (3-mercaptopropionate), trimethylolpropane tris (3-mercaptopropionate), trimethylolpropane tris (2-mercaptoacetate), pentaerythritol tetrakis (3-mercaptopropionate), pentaerytacetate (2-mercaptopropionate), pentaerythritol tetrakis yethylene glycol dimercaptoacetate and polyethylene glycol di (mercaptopropionate) as well as derivatives of these compounds substituted by halogen such as chlorine and bromine;
• (2) aromatic polythiols such as 1,2-dimercaptobenzene, 4-t-butyl-1,2-benzenedithiol, 1,3-dimercaptobenzene, 1,4-dimercaptobenzene, 1,2-bis (mercaptomethyl) benzene, 1,3 -Bis (mercaptomethyl) benzene, 1,4-bis (mercaptomethyl) benzene, 1,2-bis (mercaptoethyl) benzene, 1,3-bis (mercaptoethyl) benzene, 1,4-bis (mercaptoethyl) benzene, 1,2 -Bis (mercaptomethyleneoxy) benzene, 1,3-bis (mercaptomethyleneoxy) benzene, 1,4-bis (mercaptomethyleneoxy) benzene, 1,2-bis (mercaptoethyleneoxy) benzene, 1,3-bis (mercaptoethyleneoxy) benzene, 1,4 -Bis (mercaptoethyleneoxy) benzene, 1,2,3-trimercaptobenzene, 1,2,4-trimercaptobenzene, 1,3,5-trimercaptobenzene, 1,2,3-tris (mercaptomethyl) benzene, 1,2,4-tris (mercaptomethyl) benzene, 1,3,5-tris (mercaptomethyl) benzene, 1,2,3-tris (mercaptoethyl) benzene, 1,2,4-tris (mercaptoethyl) benzene, 1,3,5-tris (mercaptoethyl ) benzene, 1,2,3-tris (mercaptomethyleneoxy) benzene, 1,2,4-tris (mercaptomethyleneoxy) benzene, 1,3,5-tris (mercaptomethyleneoxy) benzene, 1,2,3-tris (mercaptoethyleneoxy) benzene , 1,2,4-tris (mercaptoethyleneoxy) benzene, 1,3,5-tr is (mercaptoethyleneoxy) benzene, 1,2,3,4-tetramercaptobenzene, 1,2,3,5-tetramercaptobenzene, 1,2,4,5-tetramercaptobenzene, 1,2,3,4-tetrakis (mercaptomethyl) benzene, 1,2,3,5-tetrakis (mercaptomethylbenzene), 1,2,4,5-tetrakis (mercaptomethyl) benzene, 1,2,3,4-tetrakis (mercaptoethyl) benzene, 1,2,3,5-tetrakis (mercaptoethyl) benzene, 1,2,4,5-tetrakis (mercaptoethyl) benzene, 1,2,3,4-tetrakis (mercaptomethyleno xy) benzene, 1,2,3,5-tetrakis (mercaptomethyleneoxy) benzene, 1,2,4,5-tetrakis (mercaptomethyleneoxy) benzene, 1,2,3,4-tetrakis (mercaptoethyleneoxy) benzene, 1,2, 3,5-tetrakis (mercaptoethyleneoxy) benzene, 1,2,4,5-tetrakis (mercaptoethyleneoxy) benzene, 2,2'-dimercaptobiphenyl, 4,4'-dimercaptobiphenyl, 4,4'-dimercaptodibenzyl, 2,5-toluenedithiol , 3,4-toluenedithiol, 1,4-naphthalenedithiol, 1,5-naphthalenedithiol, 2,6-naphthalenedithiol, 2,7-naphthalenedithiol, 2,4-dimethylbenzene-l, 3-dithiol, 4,5-dimethylbenzene-1 , 3-dithiol, 9,10-anthracenedimethanethiol, 1,3-di (pmethoxyphenyl) propane-2,2-dithiol, 1,3-diphenylpropane-2,2-dithiol, phenylmethane-1,1-dithiol and 2,4 di (p-mercaptophenyl) pentane;
• (3) halogenated aromatic polythiols, including chlorinated and brominated aromatic polyols, such as 2,5-dichlorobenzene-1,3-dithiol, 1,3-di (p-chlorophenyl) propane-2,2-dithiol, 3,4,5 Tribromo-1,2-dimercaptobenzene and 2,3,4,6-tetrachloro-1,5-bis (mercaptomethyl) benzene;
• (4) heterocyclic polythiols such as 2-methylamino-4,6-dithiol-sym-triazine, 2-ethylamino-4,6-dithiol-symtriazine, 2-amino-4,6-dithiol-sym-triazine, 2-morpholino -4,6-dithiol-sym-triazine, 2-cyclohexylamino-4,6-dithiol-sym-triazine, 2-methoxy-4,6-dithiol-sym-triazine, 2-phenoxy-4,6-dithiol-symtriazine , 2-thiobenzoloxy-4,6-dithiol-sym-triazine, 2-thiobutyloxy-4,6-dithiol-sym-triazine and 2-thiobutyloxy-4,6-dithiol-sym-triazine and by halogen, such as chlorine and bromine , substituted derivatives of these compounds;
• (5) polythiols which contain at least one sulfur atom in addition to the mercapto groups, including:
• (5a) aromatic polythiols such as 1,2-bis (mercaptomethylthio) benzene, 1,3-bis (mercaptomethylthio) benzene, 1,4-bis (mercaptomethylthio) benzene, 1,2-bis (mercaptoethylthio) benzene, 1,3 - bis (mercaptoethylthio) benzene, 1,4-bis (mercaptoethylthio) benzene, 1,2,3-tris (mercaptomethylthio) benzene, 1,2,4-tris (mercaptomethylthio) benzene, 1,3,5-tris (mercaptomethylthio ) benzene, 1,2,3-tris (mercaptoethylthio) benzene, 1,2,4-tris (mercaptoethylthio) benzene, 1,3,5-tris (mercaptoethylthio) benzene, 1,2,3,4-tetrakis (mercaptomethylthio ) benzene, 1,2,3,5-tetrakis (mercaptomethylthio) benzene, 1,2,4,5-tetrakis (mercaptomethylthio) benzene, 1,2,3,4-tetrakis (mercaptoethylthio) benzene, 1,2,3 , 5-tetrakis (mercaptoethylthio) benzene, 1,2,4,5-tetrakis (mercaptoethylthio) benzene and derivatives alkylated on the aromatic ring of these polythiols, and 4,4'-thiodibenzenethiol;
• (5b) aliphatic polythiols such as bis (mercaptomethyl) sulfide, bis (2-mercaptoethyl) sulfide, bis (2-mercaptopropyl) sulfide, bis (mercaptomethylthio) methane, bis (2-mercaptoethylthio) methane, bis (3-mercaptopropylthio) methane , Tetrakis (7-mercapto-2,5-dithiaheptyl) methane, 1,2-bis (mercaptomethylthio) ethane, 1,2-bis (2-mercaptoethylthio) ethane, 1,2-bis (3-mercaptopropylthio) ethane, 1 , 3-bis (mercaptomethylthio) propane, 1,2-bis (2-mercaptoethylthio) propane, 1,2-bis (3-mercaptopropylthio) propane, 1,2,3-tris (mercaptomethylthio) propane, 1,2,3 -Tris (2-mercaptoethylthio) propane, 1,2,3-tris (3-mercaptopropylthio) propane, tetrakis (mercaptomethylthiomethyl) methane, tetrakis (2-mercaptoethylthiomethyl) methane, tetrakis (3-mercaptopropylthiomethyl) methane, bis (2,3 -dimercaptopropyl) sulfide, 2,5-dimercapto-1,4-dithiane, bis (mercaptomethyl) disulfide, bis (mercaptoethyl) disulfide and bis (mercaptopropyl) disulfide, esters of thioglycolic acid and mercaptopropionic acid with these compounds, hydroxymethyl sulfide bis (2-mercaptoacetate) , Hydroxymes thylsulfidbis (3-mercaptopropionate), hydroxyethylsulfidbis (2-mercaptoacetate), hydroxyethylsulfidbis (3-mercaptopropionate), hydroxypropylsulfidbis (2-mercaptoacetate), hydroxypropylsulfidbis (3-mercaptopropionate), hydroxymethyldisulfidebisulfide bis (2-mercapto-disulfide) (2-mercapto-disulfide-bis (2-mercapto) disulfide-bis (2-mercapto-disulfide-bis-2-mercapto-disulfide-bis (2-mercapto-disulfide-bis-2-mercapto-disulfide-bis-2-mercapto-disulfide-bis (2-mercapto-disulfide-bis-2-mercapto-acetate), hydroxymethyl disulfide-bis (3-mercapto-disulfide-bis-2-mercapto-acetate)), (2-mercaptoacetate), hydroxyethyl disulfide bis (3-mercaptopropionate), hydroxypropyl disulfide bis (2-mercaptoacetate), hydroxypropyl disulfide bis (3-mercaptopropionate), 2-mercaptoethyl ether bis (2-mercaptoacetate), 2-mercaptoethyl ether bis (3-mercaptopropionate) -2,5-diolbis (3-mercaptopropionate), thioglycolic acid bis (2-mercaptoethyl ester), thiodipropionic acid bis (2-mercaptoethyl ester), 4,4'-thiodibutyric acid bis (2-mercaptoethylester), dithiodiglycolic acid bis (2-mercaptoethi-ethyl-ester) ), 4,4'-dithiodibutyric acid bis (2-mercaptoethyl ester), thiodiglycolic acid bis (2,3-dimercaptopropyl ester), thiodipropionic acid bis (2,3-dimercaptopropyl ester), Dithiodiglycolic acid bis (2,3-dimercaptopropylester) and dithiodipropionic acid bis (2,3-dimercaptopropylester) as well as derivatives of these compounds substituted by halogen such as chlorine and bromine; 4-mercaptomethyl-3,6-dithia-1,8-octanedithiol; and
• (5c) heterocyclic compounds, such as 3,4-thiophenedithiol, 2,5-bis (mercaptomethyl) tetrahydrothiophene, bis (mercaptomethyl) -1,3-dithiolane, 2,5-dimercapto-1,3,4-diazole, 2, 5-dimercapto-1,4-dithiane and 2,5-dimercaptomethyl-1,4-dithiane and derivatives of these compounds substituted by halogen such as chlorine and bromine; and tris (3-mercaptopropyl) isocyanurate; and
• (6) products of the reaction of polythiols with polyunsaturated compounds (SH excess / unsaturation), such as the addition products of 5-ethylidene-2-norbornene or diclyclopentadiene and pentaerythritol tetrakis (mercaptoacetate).

The present invention also relates to a process for the preparation of a sulfur-containing product as defined above, characterized in that at a temperature of 30 to 170 ° C a mixture of at least one polythiol (I) as defined above and at least one compound (II) converted according to the above definition into a crosslinkable product (P), the proportions of the compounds (I) and (II) being chosen such that at least essentially one thiol group of the compound or compounds (I) per mole of the compound or compounds (II) is present, and a mixture of the product (P) thus obtained and at least one compound of the formula (I) in at least substantially stoichiometric ratios of thiol groups to double bonds in a free radical manner Reacts product (P '), wherein the radicals can be generated thermally and / or by irradiation with UV or visible light or with the aid of an electron beam.

The reaction of the compounds (I) and (II) can be carried out in the presence of at least one catalyst which is used, in particular, under free radical initiators such as peroxides, for example benzoyl peroxide, p-chlorobenzyl peroxide and other diacyl peroxides, di-tert-butyl peroxide; Peroxyesters, such as t-butyl peroxy-2-ethylhexanoate or t-butyl peroxyneodecanoate; Peroxydicarbonates such as diisoproyl peroxydicarbonate or di-2-ethylhexyl peroxydicarbonate; Azo compounds such as azobisisobutyronitrile; and among Lewis acids, such as tetrafluoroboric acid, boron trifluoric acid and coordination complexes thereof with water, esters, aldehydes, alcohols, acids, ketones and ethers, such as BF ₃ · (H ₂ O) _x (x = 1 or 2), BF ₃ · C ₄ H ₉ OH, BF ₃ · 2CH ₃ COOH, BF ₃ · 2CH ₃ COOC ₂ H ₅ , BF ₃ · CH ₃ COCH ₃ , BF ₃ · O (C ₂ H ₅ ) ₂ or BF ₃ · C ₄ H ₉ OC ₄ H ₉ ; Hydrochloric acid, sulfuric acid, sulfuric acid esters such as ethyl sulfuric acid, organic sulfonic acids such as toluenesulfonic acid or butyl sulfonic acid; and amines such as triethylamine is selected. The catalyst can, for example, per thiol function of the polythiol (I) in an amount of 0.0001 to 0.5 mol in the case of peroxides, peroxyesters, peroxycarbonates and azo compounds, from 0.01 to 2.0 mol in the case of acids and Lewis Acids and from 0.05 to 0.1 mol can be used in the case of amines.

The implementation of the compounds (I) and (II) can be without solvent or in the presence of a solvent, which is in particular an aromatic, aliphatic or cycloaliphatic solvent can act, the solvent is removed at the end of the implementation.

Implementation of the polythiol (s) (2) with the product (P) can be carried out photochemically, where without a photoinitiator or photoinitiator system or in Presence of at least one photoinitiator or photoinitiator system, which can be in combination with a photoactivator, can work. You can also use UV radiation without a photoinitiator work.

In the used according to the invention Photoinitiator can be any connection the generation of radicals under the influence of ultraviolet Radiation enabled is.

• – α-Diketone, wie Benzil und Diacetyl;
• – Acyloine, wie Benzoin;
• – Acyloinether, wie Benzoinmethylether, Benzoinethylether, Benzoinisopropylether und Benzoinisobutylether;
• – Thioxanthone, wie Thioxanthon, 2,4-Diethylthio xanthon, Thioxanthon-1-sulfonsäure, Isopropylthioxanthon-4-sulfonsäure, Isopropylthioxanthon und 2-Chlorthioxanthon;
• – Benzophenone, wie Benzophenon, 4,4'-Bis(dimethylamino)benzophenon, 4,4'-Bis(diethylamino)benzophenon, 4,4'-Diethylaminobenzophenon, Mischlers Keton;
• – Propiophenone, wie 2-Hydroxy-2-methylpropiophenon, 4'-Isopropyl-2-hydroxy-2-methylpropiophenon;
• – Acetophenone, wie Acetophenon, p-Dimethylaminoacetophenon, α,α'-Dimethoxyacetoxyacetophenon, 2,2-Dimethoxy-2-phenylacetophenon, p-Methoxyacetophenon, 2-Methyl-[4-(methylthio)phenyl]-2-morpholino-1-propanon, 2,2-Diethoxyacetophenon, 4'-Phenoxy-2,2-dichloracetophenon, 2-Benzyl-2-N,Ndimethylamino-1-(4-morpholinophenyl)butanon-1, 2,2-Dimethoxy-2-phenylacetophenon, 2-Hydroxy-2-methyl-1-phenylpropanon;
• – Chinone, wie Anthrachinon, 2-Ethylanthrachinon, 2-Chloranthrachinon, 1,4-Naphthochinon;
• – alpha-Hydroxyarylketone, wie 1-Hydroxycyclohexylphenylketon;
• – Halogenverbindungen, wie Phenacylchlorid, Tribrommethylphenylsulfon, Tris(trichlormethyl)-striadin;
• – Monoacylphosphinoxide, wie 2,4,6-Trimethylbenzoyldiphenylphosphinoxid und 2,4,6-Trimethylbenzoylethoxyphenylphosphinoxid;
• – Bisacylphosphinoxide, wie Bis(2,6-dichlorbenzoyl)(4-propylphenyl)phosphinoxid, Bis(2,6-dimethoxybenzoyl)(2,4,4-trimethylpentyl)phosphinoxid, Bis(2,4,6-trimethylbenzoyl)phenylphosphinoxid und Bis(2,4,6-trimethylbenzoyl)(2,4,4-trimethylpentyl)phosphinoxid;
• – α-Sulfoketone und
• – andere Verbindungen, wie Benzildimethylketal; N,N-Dimethylaminobenzoesäureisoamylester, N,N-Dimethylaminobenzoesäureethylester, Benzoinbenzoat, 2-Hydroxy-2-methyl-1-phenylpropanon und α-Acyloximester.

Examples include:

• - α-diketones such as benzil and diacetyl;
• Acyloins such as benzoin;
• Acyloin ethers, such as benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether and benzoin isobutyl ether;
• Thioxanthones, such as thioxanthone, 2,4-diethylthio xanthone, thioxanthone-1-sulfonic acid, isopropylthioxanthone-4-sulfonic acid, isopropylthioxanthone and 2-chlorothioxanthone;
• - Benzophenones, such as benzophenone, 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone, 4,4'-diethylaminobenzophenone, mixer ketone;
• Propiophenones, such as 2-hydroxy-2-methylpropiophenone, 4'-isopropyl-2-hydroxy-2-methylpropiophenone;
• - acetophenones such as acetophenone, p-dimethylaminoacetophenone, α, α'-dimethoxyacetoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, p-methoxyacetophenone, 2-methyl- [4- (methylthio) phenyl] -2-morpholino-1- propanone, 2,2-diethoxyacetophenone, 4'-phenoxy-2,2-dichloroacetophenone, 2-benzyl-2-N, Ndimethylamino-1- (4-morpholinophenyl) butanone-1, 2,2-dimethoxy-2-phenylacetophenone, 2-hydroxy-2-methyl-1-phenylpropanone;
• Quinones, such as anthraquinone, 2-ethylanthraquinone, 2-chloroanthraquinone, 1,4-naphthoquinone;
• Alpha-hydroxyaryl ketones such as 1-hydroxycyclohexylphenyl ketone;
• - Halogen compounds such as phenacyl chloride, tribromomethylphenyl sulfone, tris (trichloromethyl) triadine;
• Monoacylphosphine oxides, such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide and 2,4,6-trimethylbenzoylethoxyphenylphosphine oxide;
• Bisacylphosphine oxides such as bis (2,6-dichlorobenzoyl) (4-propylphenyl) phosphine oxide, bis (2,6-dimethoxybenzoyl) (2,4,4-trimethylpentyl) phosphine oxide, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide and bis (2,4,6-trimethylbenzoyl) (2,4,4-trimethylpentyl) phosphine oxide;
• - α-sulfoketones and
• - other compounds, such as benzil dimethyl ketal; N, N-dimethylaminobenzoic acid isoamyl ester, N, N-dimethylaminobenzoic acid ethyl ester, benzoin benzoate, 2-hydroxy-2-methyl-1-phenylpropanone and α-acyloxime ester.

When using a photoinitiator can the above Compounds either individually as a photoinitiator or in the form of a Mixture of at least two of them can be used as a photoinitiator system. About that in addition, the photoinitiator or the photoinitiator system can be combined with at least one photoactivator.

The proportion of photoinitiator or photoinitiator system according to the invention is, for example, between about 0.5 and 10% by weight, preferably between about 1 and 5% by weight, based on the mass of the formulation of the product (s) with the polythiol (s).

Implementation of the polythiol (s) with the product (P) can also be carried out thermally, advantageously in the presence of at least one radical-generating Initiator, which is available in combination with an accelerator can, works.

The initiator exists in particular from at least one, under an organic peroxide, such as benzoyl peroxide, 2,5-dimethyl-2,5-bis (2-ethylhexylperoxy) hexane, methyl ethyl ketone peroxide, 2,4-pentanedione; a peroxydicarbonate; a peroxyester, such as tert-butyl peroxybenzoate, tert-butyl peroxy octoate, tert-amyl peroxy octoate or 2,5-diperoxyoctoate Connection. This initiator is used in particular in a proportion of 0.5 to 3 wt .-%, based on the mass of the formulation of the or of the products (P) with the one or more polythiols used.

As an accelerator of thermal Crosslinking, preferably in a proportion of 0.1 to 1% by weight, based on the mass of the formulation of the product or products (P) with the one or more polythiols, are used in particular solutions of dioctyl phthalate, inorganic or organic salts of transition metals, such as vanadium, chrome, manganese, iron, cobalt, nickel, copper, zinc, molybdenum and lead, or also from tertiary Amines, such as dimethylaniline or N, N-dimethylparatoluidine, in one organic solvents called.

When using benzoyl peroxide the peroxide initiator is preferably used as the accelerator tertiary Amine a. When using methyl ethyl ketone peroxide as a peroxide initiator a salt such as cobalt naphthenate is preferably used as the accelerator or -octoat, a.

You can also have one Photoinitiator or a photoinitiator system and optionally a photoactivator and an initiator of thermal crosslinking, use with an accelerator if necessary.

You can choose the reaction mixture the one or more polythiols (I) and the reaction product (P) in a thin layer apply to a substrate and the reaction by radical means carry out, whereby a cross-linked product (P ') is obtained in the form of a film; you but can also the reaction mixture from the or the polythiols (I) and the reaction product (P) in a mold and the Carry out a reaction in a radical way, using a networked Product (P ') in Receives the shape of a molded part, which is when using the photochemical route in the form for one for at least part of the radiation with wavelengths between 180 and 400 nm permeable Form.

The present invention relates to also a radical crosslinkable composition, the radicals thermally and / or by irradiation with UV or visible light or can be generated with the help of an electron beam, thereby characterized that they contains at least one crosslinkable product (P) as defined above.

• (a) mindestens ein vernetzbares Produkt (P) gemäß obiger Definition;
• (b) mindestens einen Vernetzer, der aus mindestens einem Polythiol (I) gemäß obiger Definition besteht, das bzw. die von dem bzw. den für die Herstellung des Produkts (P) verwendeten Polyol bzw. Polythiolen verschieden sein kann bzw. sein können;
• (c) im Fall von photochemischer Vernetzung gegebenenfalls einen Photoinitiator oder ein Photoinitiatorsystem, der bzw. das in Kombination mit einem Photoaktivator vorliegen kann;
• (d) im Fall von thermischer Vernetzung einen radikalbildenden Initiator, der in Kombination mit einem Beschleuniger vorliegen kann;
• (e) gegebenenfalls mindestens ein monomeres oder oligomeres reaktives Verdünnungsmittel;
• (f) gegebenenfalls mindestens ein Lösungsmittel oder nichtreaktives Verdünnungsmitel und
• (g) gegebenenfalls mindestens ein übliches Additiv, wie ein Pigment.

In particular, the composition contains:

• (a) at least one crosslinkable product (P) as defined above;
• (b) at least one crosslinking agent which consists of at least one polythiol (I) as defined above, which may be different from the polyol or polythiols used for the preparation of the product (P);
• (c) in the case of photochemical crosslinking, optionally a photoinitiator or a photoinitiator system, which can be present in combination with a photoactivator;
• (d) in the case of thermal crosslinking, a free radical initiator, which can be in combination with an accelerator;
• (e) optionally at least one monomeric or oligomeric reactive diluent;
• (f) optionally at least one solvent or non-reactive diluent and
• (g) optionally at least one conventional additive, such as a pigment.

The photoinitiator or photoinitiator system is selected in particular from those described above and generally in an amount of 1 to 5 wt .-%, based on the Mass of the formulation of the product (s) with the or Polythiols used.

The thermal initiator and the in combination with it, accelerators are also available selected from those described above and generally in one Amount of 0.5 to 3 wt .-% or 0.1 to 1 wt .-%, based on the Mass of the formulation of the product (s) with the or Polythiols used.

The compositions of the invention can also at least one reactive under a monomeric or oligomeric Diluents, a solvent or non-reactive diluents and a usual Additive, such as a pigment, contain selected ingredient.

The following may be mentioned as monomeric or oligomeric diluents: vinyl monomers, such as vinyl acetate, styrene, vinyltoluene or divinylbenzene; Acrylic and methacrylic acid esters, such as methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, 2-ethylhe xyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, glycidyl (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, glycerol di (meth) acrylate, glycerol tri (meth) acrylate, 1,3-propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,2,4-butanetriol tri (meth) acrylate, 1,6-hexanediol di ( meth) acrylate, 1,4-cyclohexanediol di (meth) acrylate, 1,4-benzenediol di (meth) acrylate, pentaerythritol tetra (meth) acrylate, 1,5-pentanediol di (meth) acrylate, trimethylol propane di (meth) acrylate, trimethylol propane tri (meth) acrylate, 2,2-dimethyl-3-hydroxypropyl-2,2-dimethyl-3-hydroxypropionate, isobornyl (meth) acrylate and tetrahydrofurfuryl (meth) acrylate; (Meth) acrylates of aromatic glycidyl ethers, such as bisphenol adiglycidyl ether, and aliphatic glycidyl ethers, such as butanediol diglycidyl ether, examples of which include 1,4-butanediol diglycidyl ether di (meth) acrylate, bisphenol-A diglycidyl ether di (meth) acrylate and di (meth) acrylate and di (meth) acrylate be mentioned; and acrylamides or methacrylamides, such as (meth) acrylamide, diacetone (meth) acrylamide, N- (β-hydroxyethyl) (meth) acrylamide, N, N-bis (β-hydroxyethyl) (meth) acrylamide, methylenebis (meth) acrylamide, 1,6-hexamethylene bis (meth) acrylamide, diethylene triamine tris (meth) acrylamide, bis (γ- (meth) acrylamidopropoxy) ethane and β- (meth) acrylamidoethyl acrylate.

As a solvent or non-reactive thinner be ethyl acetate, butyl acetate, Methoxypropanol, isopropanol, methyl ethyl ketone and acetone called.

The pigments are especially phthalocyanine blue or titanium dioxide.

The composition can also be used in the form of an emulsion in water or a disposition in water bring.

Optionally, the compositions of the invention stabilized. The formulation is stabilized with the help one or more radical polymerization inhibitors, the one or the usual Amounts used and among phenol type inhibitors, quinones, Phenothiazine and its derivatives, compounds with nitroxyl radicals, sterically hindered amines, aromatic nitro compounds, compounds with nitroso or N-nitroso function, phosphites and thioethers. As examples of Phenol type inhibitors its u. a. Hydroquinone, hydroquinone monomethyl ether, ortho-tert-butylphenol, 2,6-di-tert-butylphenol, 2,6-di-tert-butyl-para-nitrosophenol, para-cresol, 2,6-di-tert-butyl-para-cresol and 2,6-di-tert-butyl-para-methoxyphenol called.

Object of the present invention are also those through radical networking of the composition according to the above Products obtained in the form of films, film coatings a substrate or molded parts.

For the production of films the Composition in thin Layer applied to a substrate and radically cross-linked. The Coating compositions can can be applied to various substrates: wood, paper, chipboard, Metals, primed metals, glass, plastics, or metallized plastics. Application of the film from the composition to the substrate can by dipping, spraying, roller coating, curtain coating etc. done.

For the production of molded parts the composition is brought into a mold and radically cross-linked, which is when using the photochemical route in the form for one for at least part of the radiation with wavelengths between 180 and 400 nm permeable Form.

If the compositions of the invention hardened by ultraviolet light any suitable source, the emits ultraviolet light with a wavelength of 180 to 400 nm, like mercury arcs, Carbon arcs, Low, medium or high pressure mercury lamps, plasma arches with rotational flow and ultraviolet light emitting electroluminescent diodes. The performance of these long tube lamps is about 80 to 240 watts per cm of tube length. in the generally this is done with a thin Film of the composition coated substrate at a rate between 1 and 300 meters per minute under one or more of the led above lamps.

The following examples illustrate the present invention without limiting it in any way. In In these examples, all percentages relate to the weight, unless otherwise noted.

SYNTHESIS EXAMPLE 1

In a reaction vessel with a cooler, magnetic stirrer and Nitrogen introduction, which enables working under an inert atmosphere, 12.6 g of 5-vinyl-2-norbornene (Purity: 95%) submitted. The mixture is heated to 70 ° C. and mixed within 30 minutes over a dropping funnel containing 8.5 g of bis (2-mercaptoethyl) sulfide.

An exotherm is observed on addition and the temperature of the reaction mixture reaches 165 ° C. The reaction is followed by infrared until the -SH band at 2571 cm ^{-1 has} completely disappeared.

The product obtained has one Refractive index of 1.571 at 25 ° C.

SYNTHESIS EXAMPLE 2

The procedure is as in the synthesis example 1 using 11.2 g of 4-mercaptomethyl-3,6-dithia-1,8-octanedithiol (Purity: 93%) and 15.2 g of 5-vinyl-2-norbornene.

The achieved when adding the thiol Maximum temperature 79 ° C. The The product obtained has a refractive index of 1.579 at 25 ° C.

SYNTHESIS EXAMPLE 3

The procedure is as in the synthesis example 1 using 12.2 g of pentaerythritol tetrakis (3-mercaptopropionate) and 12.6 g of 5-vinyl-2-norbornene.

The achieved when adding the thiol Maximum temperature 134 ° C. The The product obtained has a viscosity of 0.48 Pa · s 25 ° C and a refractive index of 1.531 at 25 ° C.

SYNTHESIS EXAMPLE 4

The procedure is as in the synthesis example 1 using 12.2 g of pentaerythritol tetrakis (3-mercaptopropionate) and 12 g of 5-ethylidene-2-norbornene (purity: 99%).

The achieved when adding the thiol Maximum temperature 95 ° C. The The product obtained has a viscosity of 7.66 Pa · s 25 ° C and a refractive index of 1.5445 at 25 ° C.

SYNTHESIS EXAMPLE 5

24 g of 5-ethylidene-2-norbornene are introduced into the apparatus according to synthesis example 1 and heated to 116.degree. After this temperature has been reached, 24.4 g of pentaerythritol tetrakis (3-mercaptopropionate) are added continuously over a period of 35 minutes (41.83 g / h). The temperature is maintained at 116 ° C. for the first 5 minutes of the addition and then reduced to 84 ° C. over a period of 30 minutes (temperature gradient -1.07 ° C./min). After the addition is complete, the mixture is allowed to come back to room temperature. The absence of the -SH band at 2571 cm ^-1 indicates that all of the dithiol has been consumed. The product obtained has a refractive index of 1.5370 at 26 ° C and a viscosity of 1.16 Pa · s at 25 ° C.

SYNTHESIS EXAMPLE 6

50.1 g of 5-vinyl-2-norbornene are introduced into the apparatus according to synthesis example 1 and heated to 118.degree. After this temperature has been reached, the continuous addition of 31.1 g of 2-mercaptoethyl sulfide is started over a period of 2 hours (15.55 g / h). The temperature is kept at 118 ° C. for the first 10 minutes of the addition and then reduced to 82 ° C. over a period of one hour (temperature gradient −0.6 ° C./min). The mixture is kept at 82 ° C. until the addition of the dithiol has ended and the mixture is allowed to return to room temperature. The absence of the -SH band at 2571 cm ^-1 indicates that all of the dithiol has been consumed. The product obtained has a refractive index of 1.5610 at 24 ° C and a viscosity of 0.06 Pa · s at 25 ° C.

SYNTHESIS EXAMPLE 7

The procedure is as in Example 6 Use of 50.9 g of 5-vinyl-2-norbornene and 37.5 g of 4-mercaptomethyl-3,6-dithia-1,8-octanedithiol (Rate of addition 18.75 g / h). The product obtained has a refractive index from 1.5725 at 23 ° C and a viscosity of 0.2 Pa · s at 25 ° C.

SYNTHESIS EXAMPLE 8

The procedure is as in the synthesis example 6 using 38.9 g of 5-vinyl-2-norbornene and 37.5 g of 4-pentaerythritol tetrakis (3-mercaptopropionate) (Rate of addition 18.75 g / h). The product obtained has a refractive index of 1.5275 at 26 ° C and a viscosity of 0.27 Pa · s at 25 ° C.

Unless otherwise noted, the formulations in all of the following application examples are applied to glass using a “K Hand Coater” rod in such a way that a film thickness of 12 μm is obtained. When curing with ultraviolet light using a F450 Lamp (H-bulb) with a power of 120 W / cm from Fusion and as photoinitiators Darocure ^® 1173 (2-hydroxy-2-methyl-1-phenylpropanone-1) and Irgacure ^® 184 (1-hydroxycyclohexyl). The hardness is measured after 24 h at ambient temperature.

APPLICATION EXAMPLE 1

61.75 g of the product from synthesis example 1 are mixed with 38.25 g of pentareythritol tetrakis (3-mercaptopropionate). The refractive index of the formulation obtained is 1.564 at 25 ° C. After 2 passes under the lamp at a speed of 5 meters / min, a film with pencil hardness of 2H is obtained. When 1 g Darocure ^® 1173 and 1 g Irgacure ^® 184 are added, a dry film with pencil hardness of 4H is obtained after 2 passes under the lamp at a speed of 54 meters / min.

APPLICATION EXAMPLE 2

The formulation described above with 1 g Darocure ^® 1173 and 1 g Irgacure ^® 184 is placed in a watch glass (maximum thickness 3 mm). After 5 passes under the lamp at a speed of 5 meters / min, a transparent and flexible cross-linked material is obtained.

APPLICATION EXAMPLE 3

The formulation according to the application example 2 is with 0.5 g of cobalt octoate and 1.5 g of methyl ethyl ketone peroxide added. The formulation is molded in a watch glass. After 5 crossings under the lamp at a speed of 5 meters / min and 30 min at 130 ° C receives a flexible networked material.

APPLICATION EXAMPLE 4

37.05 g of the product of Synthesis Example 1 were mixed with 22.95 g pentaerythritol tetrakis (3-mercaptopropionate), 40 g trimethylolpropane triacrylate (sold by Sartomer under the name SR 351), 1 g Darocure ^® 1173, and 1 g of Irgacure ^® 184 offset.

After 1 pass under the lamp a dry film is obtained at a speed of 54 meters / min with the pencil hardness 2H.

APPLICATION EXAMPLE 5

The wording described above is poured into a watch glass. After 5 passes under the lamp with a Speed of 5 meters / min you get a transparent and hard cross-linked material.

APPLICATION EXAMPLE 6

62.85 g of the product of Synthesis Example 2 were mixed with 37.15 g pentaerythritol tetrakis (3-mercaptopropionate), 1 g Darocure ^® 1173, and 1 g of Irgacure ^® 184 was added. The refractive index of the formulation obtained is 1.565 at 25 ° C. After 3 passes at a speed of 54 meters / min, a dry film with the hardness H is obtained.

APPLICATION EXAMPLE 7

The formulation according to the application example 6 is poured into a watch glass. After 5 passes under the lamp with a Speed of 5 meters / min you get an opaque and flexible cross-linked material.

APPLICATION EXAMPLE 8

70.45 g of the product of Synthesis Example 2 are mixed with 29.55 g of 4-mercaptomethyl-3,6-dithia-1,8-octanedithiol, 1 g Darocure ^® 1173, and 1 g of Irgacure ^® 184th The formulation, which has a refractive index of 1.594 at 25 ° C, is poured into a watch glass. After 5 passes under the lamp at a speed of 5 meters / min, a transparent and flexible cross-linked material is obtained.

APPLICATION EXAMPLE 9

66.5 g of the product of Synthesis Example 2 were mixed with 13.9 g of 4-mercaptomethyl-3,6-dithia-1,8-octanedithiol, 19.6 g of pentaerythritol tetrakis (3-mercaptopropionate), 1 g Darocure ^® 1173, and 1 g Irgacure ^® 184 added. The refractive index of the formulation obtained is 1.579 at 25 ° C. After 1 pass under the lamp at a speed of 54 meters / min, a dry film with pencil hardness H is obtained.

APPLICATION EXAMPLE 10

The formulation according to the application example 9 is poured into a watch glass. After 8 passes under the lamp with a Speed of 5 meters / min you get a transparent and flexible networked material.

APPLICATION EXAMPLE 11

66.5 g of the product from the synthesis example 3 are mixed with 33.5 g of pentaerythritol tetrakis (3-mercaptopropionate). The refractive index of the formulation obtained is 1.531 at 25 ° C. After 1 pass under the lamp at a speed of 54 Meters / min to make a film with pencil hardness H.

APPLICATION EXAMPLE 12

1 g Darocure ^® 1173 and 1 g Irgacure ^® 184 are added to the formulation according to application example 11. The formulation is poured into a watch glass. After 5 passes under the lamp at a speed of 5 meters / min, a transparent and hard cross-linked material is obtained.

APPLICATION EXAMPLE 13

73.65 g of product from Synthesis Example 3 are mixed with 26.35 g of 4-mercaptomethyl-3,6-dithia-1,8-octanedithiol, 1 g Darocure ^® 1173, and 1 g of Irgacure ^® 184th The formulation, which has a refractive index of 1.555 at 25 ° C, is poured into a watch glass. After 8 passes under the lamp at a speed of 5 meters / min, a transparent and flexible cross-linked material is obtained.

APPLICATION EXAMPLE 14

66.5 g of the product from the synthesis example 3 are mixed with 33.5 g of pentaerythritol tetrakis (3-mercaptopropionate), 1.5 g of methyl ethyl ketone peroxide and 0.5 g of cobalt octanoate were added. The formulation is poured into a watch glass. After 1 hour at 60 ° C is obtained flexible networked material.

APPLICATION EXAMPLE 15

66.5 g of the product from the synthesis example 4 are mixed with 33.5 g of pentaerythritol tetrakis (3-mercaptopropionate). The refractive index of the formulation obtained is 1.5395 at 25 ° C. After 3 runs one gets one under the lamp at a speed of 54 meters / min Film with pencil hardness H.

APPLICATION EXAMPLE 16

The formulation according to Example 15 is treated with 1 g Darocure® 1173, and 4 g of Irgacure ^® 184th The formulation is poured into a watch glass. After 5 passes under the lamp at a speed of 5 meters / min, a transparent and hard cross-linked material is obtained.

TEST EXAMPLES 1 TO 6: Mechanical properties of cross-linked films

From the following composition: Resin + crosslinker 98% Darocure 1173 1% Irgacure 184 1% 100% cross-linked films with a thickness of 200 μm were produced.

Networking takes place through 3 passes with 5 m / min under an F450 lamp (H bulb) with an output of 120 W / cm.

Claims (19)

Product containing sulfur, obtainable by addition reaction of at least one polythiol (I) with at least one compound of the formula (II)

in which R ^{1 represents} a linear or branched aliphatic radical with an ethylenically unsaturated double bond, where R ¹ can be bonded to the norbornene ring via the latter and the ring can also contain other substituents selected from C ₁ -C ₃ alkyl, in proportions, which correspond to a thiol group of the polythiols (I) per mole of the compound or compounds (II), the thiol groups of the compound or compounds (I) mainly adding to the cyclic double bond of the compound or compounds (II) and on average, one of the two ethylenic unsaturations of a compound (II) remains free. Sulfur-containing product according to claim 1, characterized characterized it the compound of formula (II) is 5-vinyl-2-norbornene (5-vinylbicyclo [2.2.1] hept-2-ene) or 5-ethylidene-2-norbornene (5-Ethylidenebicyclo [2.2.1] hept-2-ene). Sulfur-containing product according to claim 1 or 2, characterized in that the polythiols (I) are selected from the compounds of the formula R ² - [--SH] _n , where: - R ^{2 is} an aliphatic, aromatic or heterocyclic or a combination thereof containing n-valent radical, which may contain substituents, wherein the backbone or the substituents by at least one, selected from -O- or -S- heteroatom and / or a

selected group can be interrupted, and - n stands for an integer from 2 to 6. Sulfur-containing product according to Claim 1, characterized in that the polythiols (I) are polythiols which, by adding a polythiol of the formula R ² - [--SH] _n according to Claim 3, to a compound of the formula (II) Claim 1 with an excess of thiol and under addition conditions, in which no crosslinking occurs, are available. Sulfur-containing product according to claim 1, characterized characterized that the Polythiol (I) under dimercaptoethyl sulfide, 4-mercaptomethyl-3,6-dithia-1,8-ocandithiol, Pentaerythritol tetrakis (3-mercaptopropionate) and pentaerythritol tetrakis (2-mercaptoacetate) selected is. Process for the production of a sulfur-containing Product according to one of the claims 1 to 5, characterized in that one at a temperature from 30 to 170 ° C a mixture of at least one polythiol (I) according to one of the Expectations 1 to 5 and at least one compound (II) according to one of claims 1 to 5 to a cross-linkable product (P), the proportions of the compounds (I) and (II) so that a thiol group of the compound or compounds (I) is present per mole of the compound or compounds (II), and a mixture of the product (P) thus obtained and at least a compound of formula (I) in stoichiometric ratios from thiol groups to double bonds in a radical way to one Implement product (P '), the radicals being thermal and / or by irradiation with UV or visible light or generated with the help of an electron beam can be. A method according to claim 6, characterized in that he the reaction of compounds (I) and (II) in the presence of at least one, among radical initiators such as peroxides, peroxyesters, Peroxydicarbonates and azo compounds, as well as acids and Lewis acids and Amines selected Carries out catalyst. A method according to claim 6 or 7, characterized in that that he the reaction of compounds (I) and (II) without a solvent performs. Method according to one of claims 6 to 8, characterized in that that he the reaction of compounds (I) and (II) in a solvent medium performs, being the solvent is removed at the end of the implementation. Use of the product (P) according to one of claims 1 to 5 in a radically crosslinkable composition that at least a polythiol (I) in stoichiometric conditions of thiol groups of the polythiol (s) (I) to double bonds of the product (P) contains whereby the double bonds of the product (P) are completely consumed should be to get a cross-linked product (P '). Use according to claim 10, characterized in that that he the reaction of the polythiol (s) (I) with the product (P) photochemically without a photoinitiator or photoinitiator system or in the presence of at least one photoinitiator or photoinitiator system, which can be in combination with a photoactivator, performs. Use according to claim 10 or 11, characterized in that that he the reaction of the polythiol (s) (I) with the product (P) thermal way in the presence of at least one radical initiator, which can be in combination with an accelerator. Use according to one of claims 10 to 12, characterized in that that he the reaction mixture of the one or more polythiols (I) and the reaction product (P) in thinner Layer on a substrate and the reaction to radical Carried out ways whereby a cross-linked product (P ') is obtained in the form of a film. Use according to one of claims 10 to 12, characterized in that that he the reaction mixture of the one or more polythiols (I) and the reaction product (P) brings in a shape and the reaction by radical means performs, wherein a cross-linked product (P ') is obtained in the form of a molded part, wherein is the shape using the photochemical route one for at least part of the radiation with wavelengths between 180 and 400 nm permeable Form. Radically crosslinkable composition, the Radicals thermally and / or by irradiation with W or visible Light or can be generated with the help of an electron beam, thereby characterized that they at least one crosslinkable product (P) according to any one of claims 1 to 5 contains. Crosslinkable composition according to claim 15, characterized characterized that they includes: (A) at least one crosslinkable product (P) according to any one of claims 1 to 5; (b) at least one crosslinker consisting of at least one Polythiol (I) according to one of claims 1, 3, 4 and 5; (C) in the case of photochemical crosslinking, a photoinitiator if necessary or a photoinitiator system in combination with one Photoactivator can be present; (d) in the case of thermal Networking a radical initiator, in combination can exist with an accelerator; (e) if applicable at least one monomeric or oligomeric reactive diluent; (F) optionally at least one solvent or non-reactive diluent and (g) optionally at least one conventional additive, such as a pigment. Films or moldings covering a substrate by radical crosslinking of the composition according to claim 15 or 16 available are. Process for the manufacture of the products according to claim 17 in the form of films, characterized in that the A composition according to claim 15 or 16 in a thin layer on a substrate and radically networked them. Process for the manufacture of the products according to claim 17 in the form of molded parts, characterized in that the Brings composition into a form and radically cross-links it, which is when using the photochemical route in the form for one for at least part of the radiation with wavelengths between 180 and 400 nm permeable Form.